KR101394179B1 - Thiazineindigo pigment dispersant, and pigment composition, colored composition and color filter, using the same - Google Patents

Abstract

A thiazineindigo pigment dispersant represented by Formula (1) or (2): where E denotes a basic group. A pigment composition contains a pigment material, and the thiazine indigo pigment dispersant. A colored composition contains the pigment composition and a pigment carrier. A color filter includes a filter segment prepared from the colored composition.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a thiazineindigo pigment dispersant, and a pigment composition, a coloring composition and a color filter using the same,

Figure 1 illustrates a column liquid chromatogram of the pigment dispersant B prepared in Example 1 described below.

2 illustrates a column liquid chromatogram of the pigment dispersant C prepared in Example 2 described below.

Figure 3 illustrates a column liquid chromatogram of the pigment dispersant prepared in Example 26 described below.

Figure 4 illustrates a column liquid chromatogram of the pigment dispersant prepared in Example 27 described below.

The present invention relates to a pigment dispersant which can suitably be used, for example, in printing inks, paints, resin colorants, ink-jet inks or inks for color filters, and pigment compositions and coloring compositions containing them. Further, the present invention relates to a color filter that can be used, for example, in a color liquid crystal display device or a color imaging device.

In printing inks or paints, for example, the tendency of a printing or film, such as, for example, a clear tint and a high gloss, is achieved by dispersing the pigment in a fine state to enhance the tinting strength of the pigment. Furthermore, by dispersing the pigment in a stable state, labor and energy can be saved in the production of printing inks and paints. Pigment dispersion in a stable state is generally good for storage stability.

However, in order to realize a more transparent color tone, the pigment used in printing inks and paints is generally in a finely divided form, so that the agglomeration between the pigment particles is promoted, resulting in difficulty in obtaining the aforementioned tendency.

In order to overcome these problems, a pigment dispersant is used to stabilize the pigment dispersion by enhancing the affinity between the pigment and the excipient, and various pigment dispersants have been disclosed.

For example, as a pigment dispersant, a pigment derivative in which a functional group such as an acidic group, a basic group or a phthalimido group is introduced into an organic pigment has been developed, and some advantages have been obtained (Jpn. Pat. Appln. KOKAI Publication No. 3-26767 No. 6-316676 and No. 5-331398). However, since the pigment derivative has an organic pigment as a matrix structure, strong intrinsic coloring is exhibited. Thus, there are often a number of limitations when they are used in differently colored pigments.

For example, in systems in which very fine pigment particles, such as printing inks, paints, and in particular inks for ink-jet inks and inks for color filters, are dispersed, the amount of pigment dispersing agent used must be increased to attenuate agglomeration between pigment particles and achieve age- , Which adversely affects transparency.

Furthermore, when the different pigments are mixed and dispersed, or when each of the inks made using different pigments is mixed, due to the unfavorable phenomenon that does not occur in single pigments such as viscosity increase, flooding and lifting of color, and sedimentation, Color irregularity of a colored object, and a remarkable decrease in coloring power.

It is an object of the present invention to provide a pigment dispersant which exhibits excellent dispersion performance for a wide range of pigments, which has a high dispersing power without adversely affecting color and transparency.

It is still another object of the present invention to provide a pigment composition which is free from damage to the color and transparency of the pigment and exhibits excellent dispersibility in the pigment carrier.

A further object of the present invention is to provide an ink composition which is not only excellent in fluidity and storage stability but also suitably used for printing inks, paints, ink-jet inks, or inks for color filters, To provide a coloring composition.

According to a first aspect of the present invention, there is provided a trans-thiazine indigo pigment dispersant represented by the following formula (1).

According to a second aspect of the present invention, there is provided a cis-thiazine indigo pigment dispersant represented by the following formula (2).

(Formula 1)

(2)

In the above formulas (1) and (2)

Each R ₁ independently represents an aromatic or aliphatic carbon ring which may have a substituent other than the - (E) _p - group or a group necessary to form a heterocyclic ring;

Each R ₂ independently represents an aromatic or aliphatic carbon ring which may have a substituent other than the - (E) _p - group or a group necessary to form a heterocyclic ring;

Each E independently represents a carbon ring ring containing a R ₁ or a heterocyclic ring and / or a basic group substituted on a carbon ring ring or a heterocyclic ring including R ₂ , and is represented by the following general formula (3) or :

(Formula 3)

(Formula 4)

X is _{-S-, -O-, -SO 2 -,} -CO-, -SO 2 NR-, -NRSO 2 -, -CONR-, -CH 2 NRCOCH 2 NR- , or - (CH _{2) m} NH- , Wherein each R is independently a hydrogen atom, an alkyl group of 1 to 20 carbon atoms which may have a substituent, an alkenyl group of 2 to 20 carbon atoms which may have a substituent, or an alkyl group of 6 to 20 Lt; / RTI > represents an aryl group of 1 to 10 carbon atoms, m represents an integer of 1 to 10;

a represents 0 or 1;

Y represents an alkylene group of 1 to 20 carbon atoms which may have a substituent, an alkenylene group of 2 to 20 carbon atoms which may have a substituent, an arylene group of 6 to 20 carbon atoms which may have a substituent, , An oxygen or a sulfur atom, or two or more of these groups may be bonded together directly or through a linking group selected from -NR-, -O-, -SO ₂ - and -CO- , Wherein R is as defined above;

b represents 0 or 1;

R ₃ and R ₄ each independently represent an alkyl group of 1 to 30 carbon atoms which may have a substituent or an alkenyl group of 2 to 30 carbon atoms which may have a substituent or R ₃ and R ₄ together And may form a heterocyclic group containing a nitrogen, oxygen or sulfur atom;

Z is _{-CH 2 NR'COCH 2 NR'-, -CH 2} NR'COCH 2 NR'-G-, -NR'-, -NR'-G-CO-, -NR'-G-CONR'-, _{-NR'-G-SO 2 -,} -NR'-G-SO 2 NR'-, -OG-CO-, -OG-CONR'-, -SO 2 -, -OG-SO 2 - or -OG- SO ₂ NR'-, wherein each R 'independently represents a hydrogen atom, an alkyl group of 1 to 20 carbon atoms which may have a substituent, an alkenyl group of 2 to 20 carbon atoms which may have a substituent, And each G independently represents an alkylene group of 1 to 20 carbon atoms which may have a substituent, an alkenylene group of 2 to 20 carbon atoms which may have a substituent, an alkenylene group of 2 to 20 carbon atoms which may have a substituent, Or an arylene group having 6 to 20 carbon atoms which may have a substituent;

c represents 0 or 1;

R ₅ , R ₆ , R ₇ and R ₈ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, An aryl group of 6 to 20 carbon atoms which may be optionally substituted;

R ₉ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an alkenyl group having 2 to 20 carbon atoms which may have a substituent; And

p represents an integer of 1 to 6;

According to a third aspect of the present invention there is provided a pigment composition comprising a pigment material and a trans- or cis-thiazine indigo pigment dispersant according to the present invention.

According to a fourth aspect of the present invention, there is provided a pigment composition according to the present invention, and a coloring composition comprising a pigment carrier.

Further, according to a fifth aspect of the present invention, there is provided a color filter comprising a filter segment made of a coloring composition according to the present invention.

DETAILED DESCRIPTION OF THE INVENTION

First, the trans- and cis-thiazine indigo pigment dispersants according to the present invention will be described.

The trans-thiazine indigo pigments dispersant according to the present invention is represented by the above Formula 1, and the cis-thiazine indigo pigments dispersant according to the present invention is represented by the above Formula 2.

The symbols and subscripts in the formulas (1) and (2) have the following meanings.

Each R ₁ independently represents an aromatic or aliphatic carbon ring which may have a substituent other than the - (E) _p - group or a group necessary for forming a heterocyclic ring. Likewise, each R ₂ independently represents an aromatic or aliphatic carbon ring which may have a substituent other than the - (E) _p - group or a group necessary for forming a heterocyclic ring. Examples of the substituent which the ring containing R ₁ or R ₂ may have are, for example, a halogen atom, and a nitro group, a cyano group, a trifluoromethyl group, a carbon amide group, an alkyl group, an alkoxy group, Phenoxy, phenylamino, phenylthio, acyl, acyloxy and acylamine aryl groups. The ring containing R ₁ or R ₂ is preferably an aromatic carbon ring which may have a substituent other than the - (E) _p - group, more preferably a substituent other than the - (E) _p - group And most preferably a benzene ring having no substituent other than the - (E) _p - group.

Each E independently represents a ring containing R ₁ and / or a ring-substituted basic group containing R ₂ , and is represented by the above-mentioned formula (3) or (4). Each p represents an integer of 1 to 6, preferably 1 to 4, most preferably 1 or 2.

The symbols and subscripts in the formulas (3) and (4) have the following meanings.

X is _{-S-, -O-, -SO 2 -,} -CO-, -SO 2 NR-, -NRSO 2 -, -CONR-, -CH 2 NRCOCH 2 NR- , or - (CH _{2) m} NH- . Each R is independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, most preferably 1 to 6 carbon atoms, which may have a substituent, An alkenyl group of 20 carbon atoms, preferably 2 to 10 carbon atoms, most preferably 2 to 6 carbon atoms, or an alkenyl group of 6 to 20 carbon atoms, preferably 6 to 10 carbons Atom, most preferably an aryl group of 6 carbon atoms. The subscript m represents an integer of 1 to 10.

The subscript a represents 0 (no X exists) or 1 (X exists).

Y represents an alkylene group of 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, most preferably 1 to 6 carbon atoms, which may have a substituent, 2 to 20 carbon atoms which may have a substituent, Preferably an alkenylene group of 2 to 10 carbon atoms, most preferably 2 to 6 carbon atoms, 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, which may have a substituent, Represents an arylene group having 6 carbon atoms, or a heterocyclic group containing a nitrogen, oxygen or sulfur atom. Two or more of these groups are either directly bonded together, -NR-, -O-, -SO ₂ - and it may be attached through a linking group selected from -CO-, wherein R is as defined above. Y is preferably not substituted.

The subscript b represents 0 (Y is absent) or 1 (Y is present).

R ₃ and R ₄ each independently represents an alkyl group having 1 to 30 carbon atoms, preferably 1 to 25 carbon atoms, most preferably 1 to 20 carbon atoms, which may have a substituent, Represents an alkenyl group of 2 to 30 carbon atoms, preferably 2 to 25 carbon atoms, most preferably 2 to 20 carbon atoms. R ₃ and R ₄ may together form a heterocyclic group containing a nitrogen, oxygen or sulfur atom. The substituents which R ₃ and R ₄ may have may include substituents described with respect to a ring containing R ₁ or a ring containing R ₂ as indicated above. Each R < ₃ > and R < ₄ > is preferably unsubstituted.

Z is _{-CH 2 NR'COCH 2 NR'-, -CH 2} NR'COCH 2 NR'-G-, -NR'-, -NR'-G-CO-, -NR'-G-CONR'-, _{-NR'-G-SO 2 -,} -NR'-G-SO 2 NR'-, -OG-CO-, -OG-CONR'-, -SO 2 -, -OG-SO 2 - or -OG- SO ₂ NR'-. Each R 'is independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, most preferably 1 to 6 carbon atoms, which may have a substituent, 2 Preferably from 2 to 10 carbon atoms, most preferably from 2 to 6 carbon atoms, or from 6 to 20 carbon atoms, preferably from 6 to 10 carbon atoms, which may have a substituent And most preferably an aryl group of 6 carbon atoms. Each G is independently an alkylene group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, most preferably 1 to 6 carbon atoms, which may have a substituent, 2 to 20 Preferably an alkenylene group of 2 to 10 carbon atoms, most preferably 2 to 6 carbon atoms, or an alkenylene group of 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, which may have a substituent , And most preferably an arylene group having 6 carbon atoms. The substituents that R 'and G may have may include substituents described with respect to a ring containing R ₁ or a ring containing R ₂ as indicated above. Each R 'and G is preferably unsubstituted.

The subscript c represents 0 (Z is absent) or 1 (Z is present).

R ₅ , R ₆ , R ₇ and R ₈ are each independently a hydrogen atom, an optionally substituted 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, most preferably 1 to 6 carbon atoms An alkenyl group of 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, most preferably 2 to 6 carbon atoms, which may have a substituent, or an alkyl group of 6 to 20 carbons which may have a substituent Atoms, preferably an aryl group of 6 to 10 carbon atoms, most preferably 6 carbon atoms. Each R ₅ , R ₆ , R ₇ and R ₈ is preferably unsubstituted.

R ₉ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, most preferably 1 to 6 carbon atoms, which may have a substituent, or an alkyl group having 2 to 20 Preferably an alkenyl group of 2 to 10 carbon atoms, most preferably of 2 to 6 carbon atoms. R ₉ is preferably not substituted.

In one embodiment, the thiazine indigo moiety of the trans-thiazine indigo pigment dispersant of the present invention is represented by the formula (A)

(A)

Further, in one embodiment, the thiazine indigo moiety of the cis-thiazine indigo pigment dispersant of the present invention is represented by the following formula (B)

(Formula B)

In one embodiment, in Formula (3) _{- (X) a - (Y} ) b - group is _{-SO 2 -, -SC 1 -C 6} - alkylene _{-, -SO 2 -NH-C 1} -C 6 - alkylene -, -SO ₂ -NH-phenylene-CO-, -CH ₂ NHCOCH ₂ NH-C ₁ -C ₆ -alkylene-, -C ₁ -C ₆ -alkylene-, or - (CH ₂ ) _m NH -C ₁ -C ₆ -alkylene-. In one embodiment, R ₃ and R ₄ in Formula 3 are each independently C ₁ -C ₆ -alkyl or C ₁ -C ₂₀ -alkenyl, or R ₃ and R ₄ , together with the nitrogen atom to which they are attached, A 5- or 6-membered nitrogen-containing heterocyclic ring (for example, a pyrrolidine ring or a piperidine ring) which may have a substituent such as a hydroxyl group or C ₁ -C ₆ -alkyl.

In one embodiment, -Z- group of the formula (4) _{-SO 2 -, -CH 2 NHCOCH 2} NH-, -CH 2 NHCOCH 2 NH- C 1 -C 6 - alkylene -, or -NH (C ₁ -C _6-alkylene) -SO ₂ - a. In one embodiment, R ₅ -R ₈ in Formula 4 are each independently a hydrogen atom and R ₉ is a hydrogen atom or C ₁ -C ₆ -alkyl.

Illustrative examples of the trans-thiazine indigo pigment dispersant of the present invention are represented by the following formulas (i) to (xxix) provided below.

(I) to (xxix)

Examples of cis-thiazine indigo pigment dispersants of the present invention are those in which the trans-thiazine indigo moiety is replaced with a cis-thiazine indigo moiety of the formula (B) in the formulas (i) to (xxix).

Thiazine indigo pigment dispersants can be synthesized through several synthetic routes.

For example, _a trans-thiazine indigo pigment dispersant in which the - (X) _a - (Y) _b - group in formula (3) is -SO ₂ - or -SO ₂ NH-C ₁ -C ₆ -alkylene- The trans-thiazine indigo pigments represented by the formula (A) are chlorosulfonated with chlorosulfuric acid by conventional methods to give trans-thiazines substituted with 1 to 6 chlorosulfonyl groups on benzene rings or rings of thiazine indigo Followed by reaction with an amine represented by HN (R ₃ ) (R ₄ ) or NH ₂ -C ₁ -C ₆ -alkylene-N (R ₃ ) (R ₄ ) ≪ / RTI >

The trans-thiazine indigo pigment dispersant in which the - (X) _a - (Y) _b - group in the formula (3) is -SO ₂ -NH-phenylene-CO- can be obtained by reacting the trans-thiazineindigo sulfonyl chloride shown above with an aminobenzoic acid ester , Reacting the product with an amine represented by HN (R ₃ ) (R ₄ ) (amidation), and heating the reaction product.

The trans-thiazine indigo pigments dispersant which is represented by the formula (3) - (X) _a - (Y) _b - group is -SC ₁ -C ₆ -alkylene- can be produced by reacting the trans-thiazine indigo pigments represented by the formula Brominated to obtain a trans-thiazineindigo bromide having 1 to 6 bromine atoms bonded on a benzene ring or rings of thiazine indigo, which is then reacted with HS-C ₁ -C ₆ -alkylene-N (R ₃ ) (R < ₄ >).

In the formula (3), the - (X) _a - (Y) _b - group is --CH ₂ NHCOCH ₂ NH - C ₁ -C ₆ -alkylene - in trans - thiazine indigo pigment dispersant is a trans - thiazineindigo pigment Is reacted with chloroacetamide and paraformaldehyde to obtain chloroacetamidomethyltransazine-thiazineindigo in which 1 to 6 chloroacetamidomethyl groups are bonded on benzene rings or rings of thiazineindigo, And then reacting it with an amine represented by NH ₂ -C ₁ -C ₆ -alkylene-N (R ₃ ) (R ₄ ).

In formula (3), the - (X) _a - (Y) _b - group is a C ₁ -C ₆ -alkylene- or - (CH ₂ ) _m NH-C ₁ -C ₆ -alkylene- in the presence of a Lewis acid trans represented by formula a, such as aluminum chloride-thiazine-indigo pigments Hal-C ₁ -C ₆ - alkylene _{-N (R 3) (R 4} ) , or Hal- (CH _{2) m} NH -C ₁ -C ₆ - alkylene _{-N (R 3) (R 4} ) can be produced by reacting an amine represented by the formula (wherein Hal is halogen a) (C- alkylation).

The cis-thiazine indigo pigment dispersant having the -Z- group -SO ₂ - in formula (4) can be obtained by chlorosulfonating cis-thiazine indigo pigments represented by the formula (B) by a conventional method with chlorosulfuric acid to obtain thiazine indigo Thienylindigo sulfonyl chloride substituted with 1-6 chlorosulfonyl groups on benzene rings or rings and then reacting it with an amine represented by H- (unsubstituted or substituted piperazine) .

A thiazine-thiazine indigo pigment dispersant in which the -Z- group is -CH ₂ NHCOCH ₂ NH-C ₁ -C ₆ -alkylene- or -CH ₂ NHCOCH ₂ NH- in the formula (4) is a cis-thiazineindigo The pigment is reacted with chloroacetamide and paraformaldehyde to obtain chloroacetamidomethyl cis-thiazine indigo having 1 to 6 chloroacetamidomethyl groups bonded on benzene rings or rings of thiazine indigo, Which can then be produced by reacting it with an amine represented by NH ₂ -C ₁ -C ₆ -alkylene- (unsubstituted or substituted piperazine) or NH ₂ - (unsubstituted or substituted piperazine).

The cis-thiazine indigo pigments dispersed in the formula (4) wherein the -Z- group is -NH (C ₁ -C ₆ -alkylene) -SO ₂ - are obtained by brominating the cis-thiazine indigo pigments represented by the formula (B) Thiazineindigo bromide with 1 to 6 bromine atoms bonded to a benzene ring or rings of thiazine indigo, which is then reacted with NH ₂ (C ₁ -C _{6) in} the presence of a catalyst such as palladium acetate - alkylene) -SO ₂ - (it may be generated by reaction with the amine represented by an unsubstituted or substituted piperazine).

Examples of amines that can be used in the reactions shown above include, for example, diethylamine, diethylaminoethanethiol, dimethylamine, N-ethylisopropylamine, N-methylbutylamine, N-methylisobutylamine, N Diisopropylamine, diisopropylamine, N-sec-butylpropylamine, dibutylamine, di-sec-butylamine, diisobutylamine, N-isobutyl (2-ethylhexyl) amine, dioctylamine, N-methyloctylamine, N-methyloctadecylamine, didecylamine, dihexylamine, di But are not limited to, allyl amine, N-ethyl-1,2-dimethylpropylamine, N-methylhexylamine, 2-hydroxymethylaminoethanol, dioleylamine, distearylamine, N, Dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-dimethylaminoamylamine, N, N-dimethylaminobutylamine, N, , N, N-diethylaminopropylamine, N, N-diethylaminohexylamine, N, N-diethylaminobutylamine, N, N-dimethylaminopentylamine, N, N-dibutylaminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylaminopentylamine, N, Propylamine, N, N-ethylhexylaminoethylamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, piperidine, 2 Piperidine, 3-piperidine, 3-piperidine, 3-piperidine, 4-piperazine, 2,4-lupetidine, 2,6-lupetidine, Aminoacetopiperidine, N-aminoethyl-4-piperolin, N-aminoethylpiperidine, N-aminoethylpiperidine, N-methylpiperidine, Aminoethylmorpholine, N-aminopropylpiperidine, N-amino N-methylpiperazine, N-methylpiperazine, N-methyl homopiperazine, 1-cyclopentylpiperazine, N-methylpiperazine, And 1-amino-4-methylpiperazine.

Typically, thiazine indigo pigment dispersants prepared by the above method may include compounds having different numbers of - (E) - groups substituted on the thiazine indigo moiety. Therefore, the value of "p" in formula (1) or formula (2) may be a fractional value and may be a value less than 1 on average. For example, when a pigment dispersant is prepared, the product may contain thiazine indigo wherein p is zero.

The thiazine indigo pigment dispersant of the present invention is oriented to cis or trans according to the thiazine indigo moiety used. Each of the cis and trans forms of the thiazineindigo pigment dispersant of the present invention is excellent in transparency. However, a trans-thiazine indigo pigment dispersant is more preferable because of its excellent viscosity characteristics. When the pigment material is dispersed, the trans form and the sheath form are preferably used in a ratio of 50 to 100 wt% in the trans form and 50 to 0 wt% in the sheath form, based on the total amount of the trans and the cis forms, More preferably 80 to 100% by weight of the trans form and 20 to 0% by weight of the sheath form. Most preferred is to use only the trans form.

Next, the pigment composition according to the present invention will be described.

The pigment composition according to the invention contains a pigment material and a trans- and / or cis-thiazine indigo pigment dispersant.

As the pigment material contained in the pigment composition of the present invention, various commercially available organic or inorganic pigments may be used.

Examples of the organic pigments include azo pigments, anthanthrone pigments, anthrapyrimidine pigments, anthraquinone pigments, isoindolinone pigments, isoindolin pigments, indanthrone pigments, indanthrone pigments, quinacridone pigments, quinophthalon pigments, , Diketopyrrolopyrrole compounds, thiazineindigo compounds, thioindigo compounds, pyranthrone compounds, phthalocyanine compounds, pravanthrone compounds, perinone compounds, perylene compounds, and benzimidazolone compounds. Examples of inorganic pigments include, for example, carbon black, titanium oxide, chrome yellow, cadmium yellow, cadmium red, iron oxide red, iron black, zincation, prussian blue and ultramarine blue. These pigments can be used in combination.

The thiazineindigo pigment dispersant of the present invention is particularly effective in pigments having a chemical structure similar or similar to the chemical structure of the pigment dispersant of the present invention in terms of non-cohesive, non-crystallization and good flowability. Further, it is preferable to use the pigment dispersant of the present invention for the yellow or red pigment, more preferably for the orange or red pigment, on the colored surface.

In particular, it is preferable to use the pigment dispersant of the present invention for the red pigment represented by diketopyrrolopyrrole red pigment, quinacridone red pigment, thiazineindigo red pigment and anthraquinone red pigment, Because they exhibit excellent dispersing effects on these red pigments while maintaining the color and high transparency of these pigments themselves.

The thiazineindigo pigment dispersant of the present invention may be used in an amount of preferably 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the pigment material used. When the amount of the thiazineindigo pigment dispersant of the present invention is less than 0.1 part by weight, it is difficult to obtain the effect of the thiazineindigo pigment dispersant used. If the amount of the thiazineindigo pigment dispersant of the present invention exceeds 30 parts by weight, there is no advantage of the extra pigment dispersant, and sometimes the difference between the physical properties of the pigment composition and the physical properties of the pigment becomes large, When used for inks or paints, they adversely affect the actual quality.

The thiazineindigo pigment dispersant of the present invention exhibits a sufficient dispersing effect when it is simply mixed with the pigment powder in powder form. However, (i) a method in which the pigment powder and the pigment dispersant powder of the present invention are mechanically mixed using a dissolver, a high-speed mixer, a homomixer, a kneader, a roll mill, an aerator, a sand mill or a miniature machine; (ii) a method of adding a pigment dispersant to the surface of a pigment by adding a solution containing the pigment dispersant of the present invention to a pigment suspension suspended in water or an organic solvent; (iii) dissolving the organic pigment and the pigment dispersant of the present invention together in a solvent having a strong dissolving power such as sulfuric acid, and then attaching the pigment and the pigment dispersant together using a weak solvent such as water; If you do, you will get better results.

Next, the coloring composition according to the present invention will be described.

The coloring composition according to the invention contains the pigment composition according to the invention and a pigment carrier. The pigment carrier is composed of a resin, a resin precursor or a mixture thereof. When a color filter is produced using the coloring composition of the present invention, it is preferable to use a transparent resin exhibiting a light transmittance of preferably 80% or more, more preferably 95% or more at a visible light wavelength of 400 to 700 nm Do.

The resin includes a thermoplastic resin, a thermosetting resin, and a photosensitive resin. The resin precursor includes monomers and oligomers which generate a resin by curing by irradiation with light, and these may be used alone or in combination.

The pigment carrier may be used in an amount of 30 to 700 parts by weight, preferably 60 to 450 parts by weight, based on 100 parts by weight of the pigment composition used in the coloring composition. When a mixture of the resin and the resin precursor is used as the pigment carrier, the resin may be used in an amount of 20 to 400 parts by weight, preferably 50 to 250 parts by weight, based on 100 parts by weight of the pigment composition used in the coloring composition. The resin precursor may be used in an amount of 10 to 300 parts by weight, preferably 10 to 200 parts by weight, based on 100 parts by weight of the pigment composition used in the coloring composition.

Examples of thermoplastic resins include, for example, butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, polyurethane resins, , Acrylic resin, alkyd resin, polystyrene, polyamide resin, rubber resin, cyclized rubber resin, cellulose, polyethylene, polybutadiene, and polyimide resin.

Examples of thermosetting resins include, for example, epoxy resins, benzoguanamine resins, rosin-modified maleic resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenolic resins.

Examples of the photosensitive resin include, for example, a (meth) acrylic compound having a reactive substituent such as an isocyanate group, an aldehyde group, or an epoxy group, or by introducing cinnamic acid into a polymer having a reactive substituent group such as a hydroxyl group, a carboxyl group, Polymers having photo-crosslinking groups, such as (meth) acryloyl or styryl, produced. In addition to this, it is also possible to use a hydroxyl group-containing (meth) acrylate compound such as hydroxyalkyl (meth) acrylate, a linear (meth) acrylate containing an acid anhydride such as a styrene / maleic anhydride copolymer or an- Polymers obtained by partial esterification of the polymer may also be used.

Examples of monomers and oligomers which are resin precursors include monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) (Meth) acrylates such as hexyl (meth) acrylate,? -Carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol glycidyl ether di Acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, 1,6-hexane diol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (Meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) ) Acrylates, epoxy (meth) acrylate, and various acrylic and methacrylic acid esters, such as urethane acrylate; (Meth) acrylic acid; Styrene; Vinyl acetate; Hydroxyl ethyl vinyl ether; Ethylene glycol divinyl ether; Pentaerythritol trivinyl ether; (Meth) acrylamide; N-hydroxymethyl (meth) acrylamide; N-vinyl formamide; And acrylonitrile.

The coloring composition of the present invention may contain a dispersing aid such as a surfactant or a resin type pigment dispersing agent for the dispersibility of the pigment material into the pigment carrier. The dispersion aid may be used in an amount of 0.1 to 40 parts by weight, preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the pigment composition used.

Examples of surfactants include, for example, polyoxyethylene alkyl ether sulfates, sodium dodecylbenzenesulfonates, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonates, sodium alkyldiphenyl ether disulfonates, Anionic surfactants such as triethanolamine lauryl sulfate, ammonium lauryl sulfate, stearic acid monoethanolamine, sodium stearate, sodium lauryl sulfate, monoethanolamine salt of styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate ester Active agents; Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate esters, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate Ryu; Cationic surfactants such as quaternary alkylammonium salts and their ethylene oxide adducts; Alkyl betaines such as alkyldimethylaminoacetic acid betaine; Amphoteric surfactants such as alkylimidazoline; And other surfactants such as fluorosurfactants and silicone surfactants. These surfactants may be used alone or in combination.

The resinous pigment dispersant has a pigment-affinity moiety having a property of adsorbing to the pigment and a moiety having compatibility with the pigment carrier, and adsorbs on the pigment to stabilize the dispersion of the pigment in the pigment carrier. Examples of the resinous pigment dispersant include linear or comb-shaped polyester, acrylic and urethane resins. Of course, a linear resin having a basic group, an acidic group or an aromatic group at the main chain or terminal, or a comb-shaped resin having a basic group, an acidic group or an aromatic group in the main chain or side chain is preferable.

Examples of commercially available resinous pigment dispersants include, for example, POLYFLOW No. 2. 75, No. 90 and No. SOLSPERSE 13240, 20000, 24000, 26000 and 28000 (Sumitomo 3M), MEGAFAC F171, F172 and F173 (Dainippon Ink & Chemicals, Inc.), FLUORAD FC430 and FC431 (Lubrisol Japan), DISPERBYK dispersants such as DISPERBYK 111,161,162, 163,164, 170,182, 2000 and 2001 (Byk Chemie), AJISPER dispersants such as AJISPER PB711, PB411, PB111, PB814 , PB821 and PB822 (Ajinomoto-Fine-Techno), and EFKA dispersants such as EFKA 46 and 47 (EFKA Chemicals).

The coloring composition of the present invention contains a photopolymerization initiator when the composition is cured by UV light or the like.

Examples of photopolymerization initiators include, for example, 4-phenoxy-dichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4- Acetophenone photopolymerization initiators such as methyl propane-1-one, 1-hydroxycyclohexyl phenyl ketone, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; Benzoin photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyl dimethyl ketal; Benzophenone photopolymerization initiators such as benzophenone, benzoylbenzoic acid, methylbenzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, and 4-benzoyl-4'-methyldiphenyl sulfide; Thioxanthone photopolymerization initiators such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, and 2,4-diisopropylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s- triazine, 2- (p- methoxyphenyl) (Trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho- (Trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) - (4-methoxy-naphthol- Triazine photopolymerization initiators such as 6-triazine, and 2,4-trichloromethyl (4'-methoxystyryl) -6-triazine; Borate photopolymerization initiators; Carbazole photopolymerization initiators; And imidazole photopolymerization initiators. The photopolymerization initiator may be used in an amount of 5 to 200 parts by weight, preferably 10 to 150 parts by weight, based on 100 parts by weight of the pigment composition used.

The photopolymerization initiator may be used alone or in combination, and examples thereof include a -acryloxime ester, acrylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, -Diethylisophthalophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone or 4,4'-diethylaminobenzophenone. The photosensitizer may be used in an amount of 0.1 to 60 parts by weight based on 100 parts by weight of the photopolymerization initiator used.

The coloring composition according to the present invention may contain a solvent in order to disperse the pigment material sufficiently in the pigment carrier and further to obtain a uniform coating film. Examples of solvents include, for example, cyclohexanone, propylene glycol diacetate, propylene glycol monomethyl ether, diethylene glycol diethyl ether, methyl isobutyl ketone, n-butyl alcohol, dipropylene glycol monomethyl ether, tripropylene glycol Monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, propylene glycol phenyl ether, dipropylene glycol monomethyl ether acetate , 1,3-butylene glycol diacetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, 3-methoxybutanol, Renglycol, triacetyl , 3,3,5-trimethyl-2-cyclohexene-1-one, ethylene glycol monoethyl ether,? -Butyrolactone, isoamyl acetate, ethyl 3-ethoxypropionate, propylene glycol monomethyl ether acetate, Toluene, o-xylene, m-xylene, p-xylene, methyl 3-methoxypropionate, butyl acetate, isobutyl acetate, and propyl acetate. These solvents may be used alone or in combination. The total amount of the solvent used may be 800-4,000 parts by weight, preferably 1,000-2,500 parts by weight based on 100 parts by weight of the pigment composition.

The coloring composition of the present invention may contain a storage stabilizer to stabilize the viscosity of the composition over time, and may contain an adhesion promoting agent such as a silane coupling agent to improve adhesion with the substrate.

The coloring composition of the present invention may optionally contain additives such as a thermal polymerization initiator, a plasticizer, a surface protective agent, a lubricant, a coating aid, an adhesion improver or a development improver.

The coloring composition of the present invention can be obtained by dispersing in a pigment carrier and an organic solvent the above-mentioned dispersing aid and the above-mentioned dispersing aid in an aqueous medium, using a 3-roll mill, a 2-roll mill, a horizontal sand mill, a vertical sand mill, a circular bead mill, / ≪ / RTI > and / or a photopolymerization initiator. A coloring composition containing two or more kinds of pigments can also be produced by mixing each mixture containing an organic solvent with a pigment carrier in which different pigments are finely dispersed using the thiazineindigo pigment dispersant of the present invention.

The coloring composition may be prepared by mixing and dispersing all of the components of the composition together. However, it is preferable to disperse the pigment in the resin and / or the organic solvent portion using the thiazineindigo pigment dispersant of the present invention, add the remaining components, and disperse the mixture.

Further, prior to dispersion by, for example, a horizontal sand mill, a vertical sand mill, an annular gap bead mill or an aerator, pre-dispersion using a milling mixer such as a nail or 3-roll mill, , Or treating the pigment material with a thiazineindigo pigment dispersant can be carried out. Further, after the dispersion by a bead mill or the like, post-treatment such as "aging" in which the coloring composition is stored at 30-80 DEG C for several hours to one week or post-treatment using an ultrasonic disperser or impact type beadless dispenser The stability of the coloring composition can be improved. In addition, the coloring composition of the present invention can be prepared using any dispenser or mixer, such as a microfluidizer, a high speed mixer, a homomixer, a ball mill, a roll mill, a stone mill, or an ultrasonic dispenser.

In the case of producing a color filter using the coloring composition of the present invention, dusts mixed with coarse particles of 5 mu m or more, preferably 1 mu m or more, and more preferably 0.5 mu m or more are subjected to, for example, centrifugation, sintering It is preferable to remove it by a filter or a membrane filter.

The coloring compositions of the present invention may be prepared as gravure-offset printing inks, waterless offset printing inks, silk screen printing inks, or as solvent-developed or alkali-developed resist materials.

The solvent-development type or alkali-development type resist material includes a solvent in which a thermoplastic resin, a thermosetting resin or a photosensitive resin and a monomer as a pigment carrier, a photopolymerization initiator, and a pigment composition of the present invention are dispersed.

Further, the coloring composition of the present invention can exhibit excellent dispersing effects and aging stability, and it can provide a strongly colored object when used in a wide range of printing inks, paints, inkjet inks, and plastics colorants.

In this case, the coloring composition may be a resin such as a petroleum resin, a casein, a cellak, a drying oil or a synthetic drying oil and a resin such as ethylcellosolve acetate, butyl cellosolve acetate, ethylbenzene, ethyl acetate, methanol, A solvent such as ethanol, isopropyl alcohol, butanol, ethylene glycol, glycerin, N, N-dimethylformamide, SOLVE SSO 100 (Exxon Chemical Co.), SWASOL 1000 (Maruzen Petrochemical Co.) In addition to a resin and a solvent, if necessary, using a surfactant and / or a resinous pigment dispersant together.

The color filter according to the present invention has a transparent or reflective substrate and three different colors of R (red), G (green) and B (blue) or Y (yellow), M (magenta) and C And a filter segment formed thereon. By using the coloring composition according to the present invention, filter segments of various colors can be formed by printing or photolithography.

Examples of the transparent substrate include a glass plate made of quartz glass, borosilicate glass, alumina silicate glass, surface-silica-coated soda lime glass or the like; And a resin plate made of polycarbonate, polymethyl methacrylate, polyethylene terephthalate or the like.

Examples of reflective substrates include silicon or other transparent substrates on which a thin film of aluminum, silver, silver / copper / palladium alloy, etc. is formed.

In order to produce a multi-color filter segment, the printing process is excellent in terms of mass production efficiency, and it is possible to form a pattern only by repeatedly printing and drying the pattern using the above-described various coloring compositions as printing inks Because. Furthermore, advances in printing technology have made it possible to print extremely narrow patterns with high dimensional accuracy and flatness. A preferred composition for printing is one that is resistant to drying and coagulation of the ink on a printing plate or blanket. In addition, control of the ink flowability in the printing machine is also important, and it is also possible to control the viscosity of the ink using a dispersing agent or an extender pigment.

When the filter segments of various colors are formed by photolithography, the coloring composition prepared as the above-described solvent-or alkali-developing type color resist by spray coating, spin coating, slit coating, roll coating, Lt; RTI ID = 0.0 > m. ≪ / RTI > After drying, the film is exposed to ultraviolet light through a mask having a predetermined pattern placed in contact with or not in contact with the film, if necessary. Next, the uncured region on the film is removed, for example, by immersing the film in a solvent or alkaline developer, or spraying the developer over the film through a spray nozzle, to form a desired pattern on the film. A color filter is produced by repeating similar operations for other colors. The film may be heated as needed to accelerate the polymerization of the colored resist. By photolithography, a color filter having higher precision than the printing process is produced.

During development, an aqueous solution such as sodium carbonate, sodium hydroxide or the like is used as the alkaline developer, and organic alkalis such as dimethylbenzylamine and triethanolamine may also be used. A defoaming agent or a surfactant may also be added to the developer.

In order to improve the sensitivity to ultraviolet exposure, the color resist is formed by coating a color resist with a water-soluble or alkali-soluble resin such as polyvinyl alcohol and a water-soluble acrylic resin and drying the resist to prevent polymerization inhibition by oxygen After being coated with a film, it can be exposed to ultraviolet rays.

The color filter according to the present invention can be produced by electrodeposition, transfer or other methods in addition to the above method, and the coloring composition according to the present invention can be used in any method. Electrodeposition is a method of forming a color filter by electrodepositing colloidal particles on a transparent conductive film by electrodeposition of various color filter segments using a transparent conductive film formed on a transparent substrate.

Alternatively, the transfer method is a method of previously forming a color filter layer on the surface of a removable transfer base sheet, and transferring the color filter layer onto a desired transparent substrate.

If the black matrix is formed on the transparent substrate or the reflective substrate prior to the filter segment, it is possible to further enhance the contrast of the liquid crystal display panel. Chromium, chromium / chromium oxide multilayer, and titanium nitride, and a resin film in which the light shielding agent is dispersed are used as a black matrix, but are not limited thereto. In addition, a thin film transistor (TFT) may be formed on the transparent substrate or the reflective substrate described above before forming the filter segments. Since the aperture ratio is increased in the filter segments formed on the TFT substrate, the brightness of the liquid crystal display panel is improved.

An overcoat film, a columnar spacer, a transparent conductive film, a liquid crystal alignment film and the like are formed on the color filter according to the present invention as required.

Such a liquid crystal display panel is produced by adhering a color filter to two opposing substrates by a sealant, injecting liquid crystal from an inlet of a seal region, sealing an injection port, and attaching a polarizing film or a retardation film to the outer surface of the two substrates as necessary .

The liquid crystal display panel uses color filters such as twisted nematic (TN), super-twisted nematic (STN), in-plane switching (IPS), horizontal alignment (VA) and optical compensated bend And can be used in a liquid crystal display system for performing multicolor printing.

Now, the present invention will be explained by the following examples. In the examples, "part"

Example  One

Pigment Dispersant  Synthesis of B

30 parts of the cis-thiazine indigo pigments represented by the above formula (B) were added to 300 parts of chlorosulfonic acid at room temperature. The mixture was stirred at room temperature for 7 hours and then added dropwise to 1500 parts of ice water over 15 minutes. The precipitated cis-thiazineindigo sulfonyl chloride was filtrated and washed with 3000 parts of ice water to obtain a cis-thiazineindigo sulfonic chloride compressed cake.

500 parts of ice, 500 parts of water and 47.8 parts of diethylaminoethylamine were put in a 3 L beaker, and then a cis-thiazineindigo sulfonic chloride pressed cake was added at 2-5 占 폚. Next, this mixture was heated to 60 캜 and stirred for 90 minutes. The product was filtered, washed with water and dried at 80 DEG C to obtain 43 parts of pigment dispersant B represented by the following formula (xxx).

(Formula xxx)

The molecular weight of pigment dispersant B, i.e., 696.93, was confirmed by mass spectrometry. The purity measured by high performance liquid chromatography was 61.38%. Liquid chromatography was carried out under the following conditions:

Column: Symmetry C18 5 micron from Waters;

Elution:

(A) 0.05 mol / L CH3COONH4 aq / DMF = 7/1 (v / v)

(B) DMF / water = 95/5 (v / v)

Gradient Condition:

(A) :( B) = 80/20 (v / v), holding for 5 minutes - 20 minutes - (A) :( B) = 0: 100, holding for 15 minutes;

Flow rate: 0.300 mL / min;

Injection volume: 5 占 퐇;

Oven temperature: 35 ℃.

The chromatogram of the pigment dispersant B is illustrated in FIG.

Example  2

Pigment Dispersant  Synthesis of C

100 parts of N, N-dimethylformamide and 20 parts of the pigment dispersant B synthesized in Example 1 were placed in a 200 mL four-necked flask. The mixture was stirred at 150 占 폚 for 3 hours and then added dropwise to 800 parts of water. The product was filtered, washed with water, and dried at 80 DEG C to obtain 16 parts of the pigment dispersant C represented by the formula (vii).

The molecular weight of the pigment dispersant C, i.e. 696.93, was determined by mass spectrometry. The purity measured by column liquid chromatography was 81%. Liquid chromatography was carried out under the same conditions as in Example 1. The liquid column chromatogram of the pigment dispersant C is illustrated in Fig.

Example  3

Pigment Dispersant  Synthesis of D

100 parts of N, N-dimethylformamide and 20 parts of the pigment dispersant B synthesized in Example 1 were placed in a 200 mL four-necked flask. This mixture was stirred at 90 캜 for 2 hours and then added dropwise to 800 parts of water to obtain a pigment dispersant composition ("pigment (pigment)") containing a pigment dispersant B represented by the general formula xxix and a pigment dispersant C represented by the general formula vii in a weight ratio of 1: Quot; dispersant D ").

Example  4

Pigment Dispersant  Synthesis of E

Thirty parts of the trans-thiazine indigo pigments represented by the above formula (A) and 150 parts of bromine were added to 100 parts of nitrobenzene. The mixture was stirred at 100 DEG C for 5 hours, and excess bromine was collected to obtain trans-thiazineindigo bromide.

30 parts of trans-thiazineindigo bromide and 10 parts of diethylaminoethanethiol were added to 100 parts of N, N-dimethylformamide at room temperature, and the mixture was stirred at 150 DEG C for 5 hours. The product was filtered, washed with water and then dried at 80 DEG C to obtain 38 parts of the pigment dispersant E represented by the above formula (i).

Example  5

Pigment Dispersant  Synthesis of F

27 parts of the trans-thiazine indigo pigments represented by the above formula (A) were gradually added to 325 parts of 98% sulfuric acid cooled to 0 占 폚 while being kept at 20 占 폚 or lower over 30 minutes or longer. Then, 25 parts of 2-chloroacetamide was added over 20 minutes, and then 9 parts of paraformaldehyde was added over 20 minutes. The mixture was stirred at 15 to 20 占 폚 for 4 hours and allowed to stand overnight. The reaction mixture was poured into a mixture of 750 parts of ice and 1500 parts of water. The precipitate was filtered and washed three times with 1000 parts of ice water to obtain a chloroacetamidocis-thiazine indigo pressure cake.

500 parts of ice, and 500 parts of water and 51.6 parts of 1- (2-aminoethyl) piperazine were placed in a 3 L beaker, followed by the addition of chloroacetamidocis-thiazine indigo pressure cake at 0-5 ° C. Then, this mixture was heated to 60 캜 and stirred for 2 hours. The product was filtered, washed with water and dried at 80 캜 to obtain 47 parts of a cis-thiazine indigo pigment dispersant. Further, 100 parts of N, N-dimethylformamide and 20 parts of cis-thiazine indigo pigment dispersant were added to a 200 mL four-necked flask. The mixture was stirred at 150 占 폚 for 3 hours and added dropwise to 800 ml of water. The product was filtered, washed with water, and dried at 80 DEG C to obtain 16 parts of the pigment dispersant F represented by the above formula (xxvii).

≪ Preparation of acrylic resin solution >

700 parts of cyclohexanone was placed in a separate four-necked flask equipped with a thermometer, condenser, nitrogen gas inlet, stirrer and dropping funnel, and heated to 80 ° C. The inside atmosphere of the flask was replaced with nitrogen, and then 133 parts of n-butyl methacrylate, 46 parts of 2-hydroxyethyl methacrylate, 43 parts of methacrylic acid, p-cumylphenol ethylene oxide-modified acrylate (" Aronix M110 ", manufactured by Toagosei Co., Ltd.) and 4 parts of 2,2'-azobisisobutyronitrile was added dropwise via a dropping funnel over 2 hours. The dropwise addition reaction was further continued for 3 hours to obtain an acrylic resin solution having a weight-average molecular weight of 26,000. After cooling the resin solution to room temperature, about 2 g of the resin solution was sampled and dried at 180 캜 for 20 minutes, and then the amount of nonvolatile matter was measured. On the basis of the measurement results, cyclohexanone was added to the remaining resin solution so that the concentration of the non-volatile component was 20 wt% in the resin solution to obtain a desired acrylic resin solution.

≪ Preparation of treated red pigment >

A mixture of 300 parts of diketopyrrolopyrrole (hereinafter referred to as "DPP ") red pigment (CI Pigment Red 254; available from Chiba Specialty Chemicals), 1500 parts of sodium chloride and 150 parts of diethylene glycol, The kneaded mixture was added to 5 liters of hot water and stirred for 1 hour while heating at 70 DEG C to obtain a slurry. The mixture was repeatedly filtered, washed with water to remove sodium chloride and diethylene glycol, and dried at 80 DEG C overnight to obtain 290 parts of the treated red pigment.

≪ Preparation of red / yellow mixed pigment 1 >

DPP red pigment (CI Pigment Red 254; "IRGAPHOR RED B-CF" available from Chiba Specialty Chemicals), anthraquinone red pigment (CI Pigment Red 177; "CHROMOPHTAL RED A2B" available from Chiba Specialty Chemicals) YELLOW PIGMENT E4GN-GT "available from Lanxess KK) at a weight ratio of 3: 5: 2 to obtain a red / yellow mixed pigment 1.

<Preparation of red / yellow mixed pigment 2>

DPP red pigment ("CI Pigment Red 254" "IRGAPHOR RED B-CF" available from Chiba Specialty Chemicals) and azo yellow pigment (CI Pigment Yellow 150; "YELLOW PIGMENT E4GN-GT" available from Lanxess KK) By weight to obtain a red / yellow mixed pigment 2.

<Synthesis of Pigment Dispersant A>

The compound represented by the formula (xxxi) was chlorosulfonated by a conventional method. 50 parts of the resulting compound was dispersed in 900 parts of water, and 240 parts of N, N-diethylaminoethylamine was added. The mixture was heated to 60 占 폚 and stirred at this temperature for 2 hours. The precipitate was filtered, washed with water and dried at 80 DEG C to obtain 60 parts of Pigment Dispersion A.

(Formula xxxi)

&Lt; Examples 6-25 and Comparative Example 1-14 >

The pigment, pigment dispersant A-F, acrylic resin solution and solvent (cyclohexanone) were placed in a 140 mL bottle with screw caps in the amounts shown in Tables 1a to 1c, and 150 g of zirconia beads having a diameter of 1.25 mm were added thereto. This mixture was dispersed for 10 minutes using a paint conditioner to obtain a colored composition.

&Lt; Evaluation of coloring composition >

The viscosity and thixotropic index value (TI value) of each coloring composition were measured at 25 占 폚 using a B-type viscometer.

Each coloring composition was coated on the PET film at a pre-drying thickness of 12 占 퐉 and dried at 150 占 폚 for 2 minutes to form a coating film. The color of the coating film was measured with a photometric colorimeter (SE-2000 available from Nippon Denshoku Industries) and the transparency was evaluated. Incidentally, the transparency was expressed as the difference between the saturation C of each coating film and the saturation C of the coating film prepared from each corresponding coloring composition without using the pigment dispersant of the present invention, and based on the saturation C of the composition without pigment dispersant, That is, 0 was used.

Further, each coloring composition was stored at 40 DEG C for one week and its viscosity was measured at 25 DEG C using a B-type viscometer.

(Viscosity was slightly increased, but coloring composition could be used without any problems),? (Viscosity increase was observed, and the coloring composition Could not be used), and X (marked increase in viscosity was observed and the coloring composition could not be used).

These results are shown in Tables 1a to 1c.

As shown in Tables 1a to 1c, the coloring composition using the pigment composition of the present invention has improved transparency, and in particular, the coloring composition using the trans-thiazineindigo pigment dispersant of the present invention has a low viscosity, a low thixotropy property, . In addition, the coloring composition of the present invention is excellent in storage stability over time.

*) In Tables 1a to 1c, the pigments used are as follows:

C.I. Pigment Red 202: CINQUASIA MAGENTA RT-235-D

(Available from Chiba Specialty Chemicals)

C.I. Pigment Red 122: HOSTAPERM PINK E (available from Clariant)

C.I. Pigment Violet 19: HOSTAPERM RED E5B 02 (available from Clariant)

C.I. Pigment Red 279: NOVOPERM THI RED 4G70 (available from Clariant)

Example  26

In the above formula xxix Synthesis of pigment dispersant indicated by

30 parts of the cis-thiazine indigo pigments represented by the above formula (B) were added to 300 parts of chlorosulfonic acid at room temperature. The mixture was stirred at room temperature for 7 hours and then added dropwise to 1500 parts of ice water over 15 minutes. The precipitated cis-thiazoindigo sulfonyl chloride was filtered off and washed with 3000 parts of ice water to obtain a cis-thiazineindigo sulfonic chloride-pressed cake. 500 parts of ice, 500 parts of acetone and 4-amino-N- [3- (diethylamino) propyl] benzimide were placed in a 3 L beaker, and the cis-thiazineindigo sulfonic chloride press cake was added at 2-5 DEG C did. This mixture was heated to 60 占 폚 and stirred for 2 hours. The product was filtered, washed with water and dried at 80 캜 to obtain 34 parts of a cis-thiazine indigo pigment dispersant. 34 parts of the thus obtained cis-thiazine indigo pigment dispersant and 100 parts of N, N-dimethylformamide were placed in a 200-mL four-necked flask. The mixture was stirred at 150 占 폚 for 3 hours and then added to 800 ml of water. The product was filtered, washed with water and dried at 80 ° C to obtain 24 parts of a pigment dispersant represented by the above formula (xxix).

The molecular weight of this pigment dispersant, i.e. 949.19, was confirmed by mass spectrometry. The purity measured by column liquid chromatography was 57.20%. This liquid chromatography was carried out under the same conditions as in Example 1. A liquid column chromatogram of this pigment dispersant is illustrated in Fig.

Example  27

In the above formula xx Synthesis of pigment dispersant indicated by

30 parts of the cis-thiazine indigo pigments represented by the above formula (B) were added to 300 parts of chlorosulfonic acid at room temperature. The mixture was stirred at room temperature for 7 hours and then added dropwise to 1500 parts of ice wool over 15 minutes. The precipitated cis-thiazineindigo sulfonyl chloride was filtrated and washed with 3000 parts of ice water to obtain a cis-thiazineindigo sulfonic chloride compressed cake. 500 parts of ice, 500 parts of acetone and 27 parts of diethylamine were added to a 3 L beaker, and then a cis-thiazineindigo sulfonic chloride squeeze cake was added at 2-5 占 폚. This mixture was heated to 60 占 폚 and stirred for 2 hours. The product was filtered and washed with water, and then dried at 80 DEG C to obtain 30 parts of a cis-thiazineindigo pigment dispersant. 30 parts of the thus obtained cis-thiazine indigo pigment dispersant and 100 parts of N, N-dimethylformamide were placed in a 200 mL four-necked flask. The mixture was stirred at 150 占 폚 for 3 hours and then added to 800 ml of water. The product was filtered, washed with water, and dried at 80 DEG C to obtain 24 parts of the pigment dispersant represented by the above formula (xx).

The molecular weight of this pigment dispersant, i.e. 596.76, was confirmed by mass spectrometry. The purity measured by column liquid chromatography was 87.61%. This liquid chromatography was carried out under the same conditions as in Example 1. A liquid column chromatogram of this pigment dispersant is illustrated in Fig.

The coloring composition using the pigment composition of the present invention has improved transparency. In particular, the coloring composition using the trans-thiazineindigo pigment dispersant of the present invention has low viscosity, low thixotropy property, and exhibits excellent flowability. In addition, the coloring composition of the present invention is excellent in storage stability over time.

Claims (20)

A trans-thiazine indigo pigment dispersant represented by the following formula (1). (Formula 1)

In this formula, R ₁ represents an aromatic or aliphatic carbon ring which may have a substituent other than the - (E) _p - group or a group necessary to form a heterocyclic ring; R ₂ represents an aromatic or aliphatic carbon ring which may have a substituent other than the - (E) _p - group or a group necessary to form a heterocyclic ring; E represents a carbon ring ring containing a R ₁ or a heterocyclic ring and / or a basic group substituted on a carbon ring ring or a heterocyclic ring including R ₂ , and is represented by the following formula 3 or 4: (Formula 3)

(Formula 4)

X is _{-S-, -O-, -SO 2 -,} -SO 2 NR-, -NRSO 2 -, -CONR-, -CH 2 NRCOCH 2 NR- , or - denotes a (CH _{2) m} NH-, where Each R is independently a hydrogen atom, an alkyl group of 1 to 20 carbon atoms which may have a substituent, an alkenyl group of 2 to 20 carbon atoms which may have a substituent, or an alkenyl group of 6 to 20 carbon atoms An aryl group, m represents an integer of 1 to 10; a represents 1; Y represents an alkylene group of 1 to 20 carbon atoms which may have a substituent, an alkenylene group of 2 to 20 carbon atoms which may have a substituent, an arylene group of 6 to 20 carbon atoms which may have a substituent, , An oxygen or a sulfur atom, or two or more of these groups may be bonded together directly or through a linking group selected from -NR-, -O-, -SO ₂ - and -CO- , Wherein R is as defined above; b represents 0 or 1; R ₃ and R ₄ each independently represent an alkyl group of 1 to 30 carbon atoms which may have a substituent or an alkenyl group of 2 to 30 carbon atoms which may have a substituent or R ₃ and R ₄ together And may form a heterocyclic group containing a nitrogen, oxygen or sulfur atom; Z is _{-CH 2 NR'COCH 2 NR'-, -CH 2} NR'COCH 2 NR'-G-, -NR'-, -NR'-G-CO-, -NR'-G-CONR'-, _{-NR'-G-SO 2 -,} -NR'-G-SO 2 NR'-, -OG-CO-, -OG-CONR'-, -SO 2 -, -OG-SO 2 - or -OG- SO ₂ NR'-, wherein each R 'independently represents a hydrogen atom, an alkyl group of 1 to 20 carbon atoms which may have a substituent, an alkenyl group of 2 to 20 carbon atoms which may have a substituent, And each G independently represents an alkylene group of 1 to 20 carbon atoms which may have a substituent, an alkenylene group of 2 to 20 carbon atoms which may have a substituent, an alkenylene group of 2 to 20 carbon atoms which may have a substituent, Or an arylene group having 6 to 20 carbon atoms which may have a substituent; c represents 0 or 1; R ₅ , R ₆ , R ₇ and R ₈ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, An aryl group of 6 to 20 carbon atoms which may be substituted; R ₉ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an alkenyl group having 2 to 20 carbon atoms which may have a substituent; And p represents an integer of 1 to 6; A cis-thiazine indigo pigment dispersant represented by the following formula (2). (2)

In this formula, R ₁ represents an aromatic or aliphatic carbon ring which may have a substituent other than the - (E) _p - group or a group necessary to form a heterocyclic ring; R ₂ represents an aromatic or aliphatic carbon ring which may have a substituent other than the - (E) _p - group or a group necessary to form a heterocyclic ring; E represents a carbon ring ring containing a R ₁ or a heterocyclic ring and / or a basic group substituted on a carbon ring ring or a heterocyclic ring including R ₂ , and is represented by the following formula 3 or 4: (Formula 3)

(Formula 4)

X is _{-S-, -O-, -SO 2 -,} -SO 2 NR-, -NRSO 2 -, -CONR-, -CH 2 NRCOCH 2 NR- , or - denotes a (CH _{2) m} NH-, where Each R is independently a hydrogen atom, an alkyl group of 1 to 20 carbon atoms which may have a substituent, an alkenyl group of 2 to 20 carbon atoms which may have a substituent, or an alkenyl group of 6 to 20 carbon atoms An aryl group, m represents an integer of 1 to 10; a represents 1; Y represents an alkylene group of 1 to 20 carbon atoms which may have a substituent, an alkenylene group of 2 to 20 carbon atoms which may have a substituent, an arylene group of 6 to 20 carbon atoms which may have a substituent, , An oxygen or a sulfur atom, or two or more of these groups may be bonded together directly or through a linking group selected from -NR-, -O-, -SO ₂ - and -CO- , Wherein R is as defined above; b represents 0 or 1; R ₃ and R ₄ each independently represent an alkyl group of 1 to 30 carbon atoms which may have a substituent or an alkenyl group of 2 to 30 carbon atoms which may have a substituent or R ₃ and R ₄ together And may form a heterocyclic group containing a nitrogen, oxygen or sulfur atom; Z is _{-CH 2 NR'COCH 2 NR'-, -CH 2} NR'COCH 2 NR'-G-, -NR'-, -NR'-G-CO-, -NR'-G-CONR'-, _{-NR'-G-SO 2 -,} -NR'-G-SO 2 NR'-, -OG-CO-, -OG-CONR'-, -SO 2 -, -OG-SO 2 - or -OG- SO ₂ NR'-, wherein each R 'independently represents a hydrogen atom, an alkyl group of 1 to 20 carbon atoms which may have a substituent, an alkenyl group of 2 to 20 carbon atoms which may have a substituent, And each G independently represents an alkylene group of 1 to 20 carbon atoms which may have a substituent, an alkenylene group of 2 to 20 carbon atoms which may have a substituent, an alkenylene group of 2 to 20 carbon atoms which may have a substituent, Or an arylene group having 6 to 20 carbon atoms which may have a substituent; c represents 0 or 1; R ₅ , R ₆ , R ₇ and R ₈ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, An aryl group of 6 to 20 carbon atoms which may be substituted; R ₉ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an alkenyl group having 2 to 20 carbon atoms which may have a substituent; And p represents an integer of 1 to 6; A pigment composition comprising a pigment material and a trans-thiazine indigo pigment dispersant according to claim 1. A pigment composition comprising a pigment material and a cis-thiazine indigo pigment dispersant according to claim 2. The pigment composition according to claim 3, wherein the pigment material comprises a diketopyrrolopyrrole red pigment, a quinacridone red pigment, a thiazineindigo red pigment, or an anthraquinone red pigment. 5. The pigment composition according to claim 4, wherein the pigment material comprises a diketopyrrolopyrrole red pigment, a quinacridone red pigment, a thiazineindigo red pigment, or an anthraquinone red pigment. The pigment composition according to claim 5, wherein the pigment material further comprises a yellow pigment. 7. The pigment composition according to claim 6, wherein the pigment material further comprises a yellow pigment. A coloring composition comprising the pigment composition of claim 3 and a pigment carrier. A coloring composition comprising a pigment composition according to claim 4 and a pigment carrier. A coloring composition comprising a pigment composition according to claim 5 and a pigment carrier. A coloring composition comprising the pigment composition of claim 6 and a pigment carrier. A coloring composition comprising the pigment composition of claim 7 and a pigment carrier. A coloring composition comprising the pigment composition according to claim 8 and a pigment carrier. A color filter comprising a filter segment made of the coloring composition according to claim 9. A color filter comprising a filter segment made of the coloring composition according to claim 10. A color filter comprising a filter segment made of the coloring composition according to claim 11. A color filter comprising a filter segment made of the coloring composition according to claim 12. A color filter comprising a filter segment made of the coloring composition according to claim 13. A color filter comprising a filter segment made of the coloring composition according to claim 14.

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